Unveiling the coexistence of cis- and trans-isomers in the hydrolysis of ZrO: A coupled DFT and high-resolution photoelectron spectroscopy study.

High-resolution anion photoelectron spectroscopy of the ZrOH and ZrOD anions and complementary electronic structure calculations are used to investigate the reaction between zirconium dioxide and a single water molecule, ZrO + HO. Experimental spectra of ZrOH and ZrOD were obtained using slow photoelectron velocity-map imaging of cryogenically cooled anions, revealing the presence of two dissociative adduct conformers and yielding insight into the vibronic structure of the corresponding neutral species. Franck-Condon simulations for both the cis- and trans-dihydroxide structures are required to fully reproduce the experimental spectrum. Additionally, it was found that water-splitting is stabilized more by ZrO than TiO, suggesting Zr-based catalysts are more reactive toward hydrolysis.